CA2127922A1

CA2127922A1 - Fertilizing preparation improving the extraction of phosphor for plants

Info

Publication number: CA2127922A1
Application number: CA002127922A
Authority: CA
Inventors: Thomas Ahlnas; Stephan Vermeulen; Anders Weckman
Original assignee: Kemira Oyj
Current assignee: Kemira Oyj
Priority date: 1993-07-15
Filing date: 1994-07-13
Publication date: 1995-01-16
Also published as: US5482529A; NL9401171A; FI93947B; FI933215L; FI93947C; FI933215A0; ITTO940572A0; IT1266166B1; ES2087024B1; NL194980C; ES2087024A1; ITTO940572A1

Abstract

A controllably active fertilizing preparation in the form of an emulsion-suspension or an emulsion, is comprised of: a) 30-90 % by weight of mixtures containing plant nutrients, b) 5-50 % by weight of water, c) 2-20 % by weight of an oleophilic organic substance, d) 1-25 % by weight of a surface-active substance, and e) 0.1-10 % by weight of an acid or its mixture, salt or anhydride. The acid component improves the extraction of phosphor.

Description

- - ~12792~
FERTILIZING PREPARATION I~iPROVING THE E~TRACTION OF PHOSPHOR
FOR PL~NTS

The invention relates to a controllably active fertilizing preparation which is in the form of an emulsion-suspension or emulsion, comprising:
a) 30-90 % by weight of a compound containing plant nutrient, b) 5-50 % by weight of water, ~ -c) 2-20 % by weight of an oleophilic organic substance, and d) 1-25 % by weight of a surface active substance.
The invention further relates to the use of such a fertilizer mixture as a fertilizer by adding it to the soil.

It is well-known that plants can only partially utilize the phosphor given as a fertilizer. The ls direct admission thereof may only be about 10-30% of the given amount while a part of it is bound to the soil in a form difficult to be assimilated by plants. Therefore, the total concentration of low-soluble phosphor in cultivated land is high in Finland and many European countries. The binding capability of phosphor varies depending on the soil type, but especially soils containing iron bind it very effectively.
US defence publication T969 003 discloses an emulsion composition consisting of liquid plant nutrient, organic solvent unmixable with water, and a w/o type surface active substance. The composition contains about 13-26 % by weight fertilizer, about 60-81 % by weight of water, about 4-13 % by weight of oil, and about 0.2-1.4 % by weight of w/o type 2s surface active substance (examples 4, 6, and 7). The formulation thus relates to liquid fertilizer compositions in which the plant nutrient is dissolved in a large amount of water.
The amount of fertilizer is very large and difficult to handle considering its nutritional value. This emulsion composition does not contain a component activating low-soluble phosphor compounds.
-FI application publication 913 257 discloses a controllably active fertilizing preparation which is in the form of a paste, containing plant nutrient, water, oii, and a surface active substance. It does not activate, per se, low-soluble phospor compounds.

JP application publication 4-31382 discloses the use of chelating water soluble carboxylic acids and their salts for activating phosphor compounds combined with soil. According to the publication, these activating substances can be added to the soil either as they are, or together with compound fertilizers, or adsorbed in a carrier.

The solution according to the JP application has the drawback that the adding of acids or

2 2127922 their salts to the soil as aqueous solutions causes them to drain vft, whereby a major part uf them will be lost. If they àre added in a liquid form into solid fertilizer, the fertilizer will be decomposed mechanically.

The above drawbacks are now eliminated by a new fertilizing preparation which is mainly characterized by what is said in the characterizing clause of Clairn 1. When alternatives were studied for rendering the use of phosphor more effective in fertilizing preparations and for activating phosphor bound to the soil, it was found that the adding of organic and/or inorganic acids to the fertilizing preparations improved the phosphor assimilation of plants.
o It was thus realized that if the fertilizing preparation is in the form of a paste, suspension-emulsion, or emulsion, containing plant nutrient, water, an oleophilic organic substance, and a surface active substance, an acid or acid-forming substance can be added to it without having the components of the fertilizing preparation decomposed mechanically. The fertilizing preparation retains acid or acid-forming substance and thus prevents them from 1S draining off from the soil.

Another advantage of the invention is that, instead of a highly refined source of phosphor, a cheaper raw material may be used, for instance, rock phosphate (apatite) which is converted, by the effect of the acid contained in the preparation, into a form more usable by plants.

In addition, the acids may be able to improve the trace element assimilation of plants.

The fertilizing preparation according to the invention is either in the form of an emulsion-~5 suspension or an emulsio~. It is preferably in the form of a paste.

The acid concentration of the fertilizing preparation is 0.1-10 % by weight, based on the total arnount of the fertilizing preparation. The concentration greatly depends on the acid or acid derivative used and is according to one embodiment preferably 2-6 % by weight.
According to one embodiment the acid is a C1-C1o-monocarboxylic acid, hydroxycarboxylic acid, or dicarboxylic acid, or a combination, salt or anhydride thereof.
Typical monocarboxylic acids include forrnic acid, acetic acid, and propionic acid. Typical hyd~oxycarboxylic acids include citric acid and tartaric acid. Typical dicarboxylic acids include oxalic acid, adipic acid, and maleic acid. According to another embodiment the acid is an organic sulphonic acid such as p-toluenesulphonic acid.

Accordirlg to a third embodiment the acid is a polybasic carboxylic acid such as a polymeric carboxylic acid. Examples thereof include anionic polyelectrolytes, preferably polyacrylic acid, polymethacrylic acid, and oc-hydroxyacrylic acid. Good results have been : :: . , : . ~ .: .~, . .: - .. , :

~ 3 212792~
accomplished with hydrolyzed polyacrylic amide.

According to a fourth embodiment the acid is inorganic and preferably a mineral acid like nitric acid or phosphoric acid.

In addition to the free acid, the advantageously effecting acid can be a dissociable derivative of organic acids such as a salt or an anhydride, or a combination of the above-mentioned acids~ Typical useful acid compounds include oxalic acid - citric acid - formic acid, nitric acid - phosphoric acid, and oxalic acid -citric acid - forrnic acid - oxalic acid.
~ , The plant nutrient used in the invention is preferably fertilizer raw material, which together with the water component of the fertilizing preparation forms a compound which is near the ~-saturation point and preferably above it. ~ the latter case the aqueous phase of the fertilizing preparation contains a compound containing plant nutrients or a precursor thereof ls in crystal form. Solid plant nutrient can also be suspended in the oil phase or in the oil/water interface.

An advantage of the fertilizing preparation of the present invention is that its emulsion structure essentially remains, independent on the temperature and even after cooling the mixture.

The plant nutrient used in the fertilizing preparation can be any fertilizer raw material known in the art such as N, K and/or P fertilizers. According to an preferred embodiment, the plant nutrient is based on the cations NH4+, K+, Ca2+, Mg2+: the anions NO3, Cl-, S042-, phosphates, polyphosphates; and/or urea and/or trace element nutrients. In addition to urea, concrete compounds include ammonium nitrate, ammonium phosphates such as diammonium phosphate, potassium chloride, superphosphates, and alkaline earth oxides.
Because the fertilizing preparation of ~he invention contains phosphor-activating acid or acid derivative, the preparation can contain a more low-soluble phosphor compound than usually. Therefore, it is advantageous if the preparation contains a low-soluble phosphor compound, preferably apatite.

The fertilizing preparation improving the assimilation of phosphor contains about 30-90 %
by ~eight, preferably about 60-80 % by weight percent of a compound containing a plant nutrient. ~-The amount of water in the fertilizing preparation is about 5-50 % by weight, preferably ; ~ -about 1~30 % by weight. ~ -The oleophilic organic substance used in the fertilizing prepara~ion improving the .~. : -:

~, . . . . . . . . . ... . . .

4 2127~-~2 assimilation of phosphor according to ~he invention is pre~er.lbly a non-phytotoxic oil and most preferably a vegetable-based oil such as rubseed oil, soybean oil, sunflower oil, palm oil, coconut oil, corn oil, or rapeseed oil, or a mixture of these oils. The amount of oil is about 2-20 % by weight, preferably about 2-6% % by weight of the fertilizing preparation improving the assimilation of phosphor.

The quantity and quality of the surface-active substance have a crucial effect on the usability of the fertilizing preparation according to the invention. The above-mentioned surface-active substance is preferably of ~he w/o type and most preferably a lecithin. Other usable w/o type surface-active substances include the ester of a polyol and a fatty acid, or a derivative of the ester such as an oily or fatty monoglyceride thereof. Other w/o type surface-active substances include propylene glycol monostearate, sorbitan sesquioleate, glycerol monostearate, acetylated monoglyceride (stearate~, decaglyserol octaoleate, diethylene glycol monostearate, sorbitan monooleate, propylene glycol monolaurate, s sorbitan monostearate, polyoxyethylene fatty alcohol ether, and lignosulphonate. The surface-active substance can also be an emulsifier mixture.

An important characteristic of a surface-active substance is its capability to create an emulsion. The fertilizer mLxture according to the invention contains about 1-25 % by weight and preferably about 2-6 % by weight of a surface-active substance. Instead of the water, the oleophilic substance, and the surface-active substance, technical mixtures, such as by-products of various processes, containing at least two of ~ese components can be used. Suitable substances are distiller's grain, molasses, and vinasses.

2s Nitrification inhibitors, slowly soluble or slowly decomposing plant nutrients, growth improving components, plant-protecting agents, growth hormones, and/or soil-irnproving components can also be added to the fertilizing preparation.

As previously mentioned, the fertilizing preparation according to the invention which is in the form of a paste or emulsion-suspension is advantageously used as a fertilizer by adding it onto soil as it is, i.e. in the form of a paste or emulsion-suspension. Thus the advantage is accomplished in that the storing, transportation, and spreading equipment of liquid manure which already exist in farms, can be used to spread it.

. . , 3s A few embodiments are disclosed in the following which are meant to be merely illustrative of the present invention.

Examples 1 to 7 and 9 to 19 describe the preparation of paste fertilizers.

Examples 8 and 20 describe growing tests carried out in a tray with the aid of the . .

ferrilizers. 21 2 7 9 2 ~

Examples 21 to 24 describe tne preparation of the fertilizers using different formulas.

s All the percentages are on a weight basis, if not otherwise mentioned.

F.x,~m~L 1 A mixture containing 60g of water and 200g of dry ground fertilizer comprising nitrogen, phosphor, and potassiurn in a ratio of 15-6-12 is ground by a ball mill. A mixture is added o to thus forrned sludge, containing 20.7g of rapeseed oil and 20.7g of surface-active substance (soy lecithin) and is emulsified using a rod mixer. Finally, 20g of citric acid is added to the product. The resulting product is paste-like.

Examples 2-S
The paste fertilizers were prepared in the marmer described in Example 1, the formulas are in Table 1.

Ta~le 1 Portion, % by weig~t ~escontai~iDg Orgamc Example plantDubients Water - ~ubstance Acids 62.2 18.7 12.~ Sokalal~* 6.2

3 63.9 19.3 13.2 ~tol~e 2s ~ulph.acid 3.6

4 65.6 16.4 13.1 ~g-aceta~e 4 g 68.3 11.2 13.7 amm.p~ on. 6.
* Sokalan is a mixture of C~-C4-dicarboxylic acids. ~--F,~anlple 6. Preparatinn of a fertilizer A mixture containing 25g of water, 27.2g of amrnonium nitrate, 20.8g of urea, 49.2g of apatite, 38.2g of potassiun sulphate, 2.6g of citric acid, 2.6g of oxalic acid, and 1.3g of formic acid is ground by a ball mill. 16.7g of oil and 1.67g of soy lecithin are added to the resulting suspension and the mixnlre is emulsified using a rod mixer. The product is paste-3s lilce.

E~a~l~ 7 A mixture containing 28g of water, 25.6g of ammonium nitrate, 19.4g of urea, 46.4g of apatite, 35.8g of potassium sulphate is ground by a ball mill. 12.3g of oil and 12.3g of soy ~o lecithin are added to the resulting suspension and the mixture is emulsified using a rod -:: -, ;
.. - .. - - -: . . . ..
, : , -, . ... .. .

mixer. Finally, 12.6g of concentrated nitric acid is added. The product is paste-like, ExampLe 8, growirl~ tests Seven liters of moist soil was portioned into BaumaM-trays. Paste-like fertilizers were s spread out using disposable syringes of 10 ml each, The used amounts of fertilizers (200 mg/l of N, 40 mg/l of P, 200 mg/l of K) were counted per 7 liters of soil, Solid chen~icals (KNO3, NH4NO3, KCI) for balancing the nutrients were used by those test participants who received granular test fertilizers, The amounts of nutrients for those test participants who had received paste-like test fertilizers were mainly balanced using NK-paste, The plant o grown in the trays was rye-grass, The grass harvests were dried in an incubator and their phosphor contents were determined, Granular fertilizer (Examples 1-5) in accordance with tbe present practice or granular fertilizer containing apatite (Examples 6-7) were used as comparison, The results are in Table 2, Table 2 Fertil, P-intake of P-intake of 1 +2 P-intake % of the 1, harvest 2, harvest comparison mgltray mgltray - ~
NPK-granule* 80,1 48.2 128.30 100 - -Example 1 87.6 47.9 13S.50 106 Example 2 84.8 49.3 134.10 105 Example 3 81.9 56.3 138.20 108 -2s Example 4 84.8 53.8 138.60 108 ' ~ ' Example 5 84.4 54.3 138.70 108 NPK-granule, P as apatite* 54.4 40.4 94.80 lOû
Example 6 59.6 45.5 105.10 111 . . , Example 7 68.9 46.7 115.60 122 (* = comparison) The test results indicate that the extraction of phosphor for plants has improved. Especially for the fertilizer containing apatite, the effect of acid is considerable.
Fl-.orl~ 9 ~W~
A mixture containing 12.5kg of water and 50kg of dry, ground fertilizer, which contains nitrogen, phosphor and potassium in the ratio of 15-6-12, is ground in a bead mill at the ~` 7 2127922 temper~ture of ~0C. Tll~ re~ulting suspension is pumpe~l into an emulsifying appilra~us, where a mi~cture at 40C temperanlre is added to it, containing S kg of rapeseed oil and S
kg of surface-active substance (soy lecithin), and emulsified. Finally, 500g of acid compound is added to the product, containing oxalic, sitric, and folmic acids in a weight ratio of 1: 1: 1. The resulting product is paste-like.

Examples 10-16: Preparation Off~
Emulsion fertilizers were prepared in such a way that suspensions were first made, using the bead mill, of water and the fertilizing powder according to Example 1, then rapeseed oil and lecithin was added, it was emulsified, and finally different organic acids, mixtures or salts thereof, unorganic acids or mixtures of unorganic and organic acids were mixed with the product. The formulas are shown in Table 3.
Table 3 Portion, % by weight Mixtures containing Organic Example plantnutrients Water substance Acids Comparative test 68.9 17.2 13.9 -68.4 17.1 13.7 Nitric acid 0.6 Phosphoric acid 0.15 -2s - ~
11 65.0 16.1 15.4 Nitric a. 2.9 -Phosph.a. 0.7 -: -:
1'~ 69.9 12.6 14.0 Oxalic a. 1.4 Ci~ic a. 1.4 Formic a. 0.75 :
13 69.4 15.3 13.9 Phosph.a. 0.69 -- -Oxalic a. 0.28 ~ ~ -Citric a. 0.28 Formic a. 0.14 14 70.4 14.8 14.1 Sokalan 0.35 -~
~ - Acetic a. 0.35 68.5 14.4 13.7 Sokalan 2.7 Acetic a. 0.68 16 68.8 17.2 13.9 Hydrolyzedpoly~
acrylic arnide 0.1 - . ., - -, : , . . : . - - .

` - 8 2~27922 E~le 17: Preparation of a ~ertilizer A mixture con~aining 5kg of water, 18.5kg of nitrochalk (KAS), llkg of urea, and 20.5kg of potassium sulphate is ground by a bead mill at the temperature of 40C. The resulting suspension is pumped into the emulsifying apparatus where a mixture at 40C is added to s it, containing 5kg of rapeseed oil and 5kg of soy lecithin. Finally, 2.5kg of citric acid is added to the product.

Emulsion fertilizers were prepared in such a way that suspensions were first made, using the bead mill, from water and the fertilizing powder according to Example 17, the rapeseed oil and lecithin were added, it was emulsified and finally, a mixture of organic acids was added to the product. The formulas are shown in Table 4.
~klQ
Portion, % by weight Mixtures containing Organic Example plant nutrients Water substance Acids Comp. 74.7 10.4 14.9 18 76.3 7.6 15.3 Oxalica. 0.3 Citric a. 0.3 Formic a. 0.1 19 74.1 7.4 14.8 Oxalic a. 1.5 Citric a. 1.5 Formic a. 0.75 E~l~ 20: Growing tests 3.5 Iiters of dry sandy soil was transferred to trays of 5 liters each. The soil was fertilized using the fertilizers according to examples nn and a comparative fertilizer in such a way that the nutrient amounts in the trays mg/kg of soil were as follows: 300 mg/kg of N, 300 mg/kg of P2Os, and 300 mg/kg of K2O. The grass grown in the trays was rye-grass. The 3s grass in the trays was cut after 4 weeks and again after 7 weeks of planting. The cut grass samples were dried and dry weights and phosphor contents were determined on them. The extraction of phosphor of the plants was compared to corresponding paste-like fertilizers which had no acids added thereto. The results are in Table 5.

---` 92127922 Takle 5 Fertilizer P-intake of P-intake of 1 +2 % of the 1. harvest 2. harvest P-intake comparison mgltray mgltray s NPK-paste* 31.1 37.6 68.72 100 Example 9 49.5 42.2 91.70 133 Example 10 35.2 43.6 78.80 115 Example 11 42.2 46.5 88.70 129 lo Example 12 48.3 46.9 95.20 139 Exarnple 13 46.6 41.3 87.90 128 Example 14 39.4 37.8 77.20 112 Example 15 39.6 45.8 85.40 124 Example 16 56.8 47.3 104.1 152 ~ -:
NK-paste* 14.8 21.8 36.60 100 :
Example 17 21.4 20.9 42.30 116 --Example 18 17.2 21.6 38.80 106 Exarnple 19 25.4 20.4 45.80 125 (*= comparison) -~
-The results show that the extraction of phosphor OI plants was improved considerably by fertilizers containing acid components, as much as 50% at the most. The test which was 2s carned out using NK-pastes showed that acids improved the utilization of phosphor in soil.

Exa~Ls 21-24. Prepar~ion of fer~iliz~s usin~ different fo~las.
The raw material contairling plant nutrients were ground, mixed with water, distiller's grain or vinasses, by a ball mill. Oil and lecithin were added when needed and emulsifying was ::
carried out by a rod mixer. The formulas are in Table 6.

~:
. . ~

- '~

, ~ . - - . . , -` 2127~2~

I~) Table ~
Portion, % by weight Compo~e~t:Example 21 ~;xample 22 Example 23 Example 24 S ~_~
Po~rdeled fe;r~
~15-fi 12 41.6 49 19 10 N~No3 17.9 ~Iea. 13.6 Apa~te 32.4 1~2S04 25.1 ~Va~ 9.6 11 4.5 1~; Distille,r'8 gIa~ll (36 9~ dry ma~ter) 31.4 32~6 V~a~ses 8 4.5 Oil 8 3.4 I~cithin 8 3.4 20 Ci~ ~d S
N~uic a~id 2 2

Claims

1. A controllably active fertilizing preparation which is in the form of an emulsion-suspension or an emulsion, comprising of:
a) 30-90 % by weight of mixtures containing plant nutrients, b) 5-50 % by weight of water, c) 2-20 % by weight of an oleophilic organic substance, and d) 1-25 % by weight of a w/o type, surface-active substance, characterized in that it further comprises:
e) 0.1-10 % by weight of acid, or a mixture or an anhydride thereof.

2. A fertilizing preparation according to Claim 1, c h a r a c t e r i z e d in that it is in the form of a paste.

3. A fertilizing preparation according to Claim 1 or 2, c h a r a c t e r i z e d in that the acid is a C1-C10-monocarboxylic acid, hydroxycarboxylic acid, or a dicarboxylic acid, or a salt, an anhydride, or a mixture thereof.

4. A fertilizing preparation according to Claim 1 or 2, c h a r a c t e r i z e d in that the acid is an inorganic acid, preferably nitric or phosphoric acid.

5. A fertilizing preparation according to Claim 1 or 2, c h a r a c t e r i z e d in that the acid is an anionic polyelectrolyte, preferably polyacrylic acid, polymethacrylic acid, or a mixture or derivative thereof.

6. A fertilizing preparation according to Claim 5, c h a r a c t e r i z e d in that the acid is a hydrolyzed polyacrylic amide.

7. A fertilizing preparation according to any of the preceding Claims, c h a r ac t e r i z e d in that it comprises about 0.10-10 % by weight of acid, or a mixture, salt or an anhydride thereof.

8. A fertilizing preparation according to any of the preceding Claims, c h a r ac t e r i z e d in that it contains low-soluble phosphor such as apatite.

9. A fertilizer according to any of the preceding Claims, c h a r a c t e r i z e d in that it contains at least 60 % by weight of a mixture containing plant nutrient.

10. A fertilizer according to any of the preceding Claims, c h a r a c t e r i z e d in that it contains 80 % by weight of a mixture containing plant nutrient, at the most.

11. A fertilizing preparation according to any of the preceding Claims, c h a r a c t e r i z e d in that it contains 6 % by weight of an oleophilic, organic substance, at the most.

12. A fertilizing preparation according to any of the preceding Claims, c h a r a c t e r i z e d in that it contains 6 % by weight of a surface-active substance, at the most.

13. A fertilizing preparation according to any of the preceding Claims, c h a r a c t e r i z e d in that it contains 40 % by weight of water, at the most.

14. A fertilizing product according to any of the preceding Claims, c h a r a c t e r i z e d in that the mixture containing plant nutrients is a fertilizing raw material which together with the water component of the fertilizing mixture forms a compound which is near the saturation point or preferably above it.

15. A fertilizing preparation according to any of the preceding Claims, c h a r a c t e r i z e d in that the plant nutrient is based on cations NH4+, K+, Ca2+, Mg2+; on anions NO3-, Cl-, SO42-, phosphates, polyphosphates, and/or on urea and/or on micro nutrients.

16. A fertilizing preparation according to any of the preceding Claims, c h a r a c t e r i z e d in that the oleophilic organic substance is a non-phytotoxic oil.

17. A fertilizing preparation according to Claim 16, c h a r a c t e r i z e d in that the non-phytotoxic oil is chosen from the following oils: rubseed oil, sunflower oil, palm oil, coconut oil, corn oil, or rapeseed oil, or a mixture of these oils.

18. A fertilizer according to any of the preceding Claims, c h a r a c t e r i z e d in that the surface-active substance is a w/o type substance, preferably lecithin, an ester of polyol and fatty acid or a derivative thereof such as an oily or fatty monoglyceride, or a lignosulphonate.

19. A fertilizing preparation according to Claims 1-4, c h a r a c t e r i z e d in that the oleophilic substance, which is also surface-active, is in the form of distiller's grain.

20. A fertilizing preparation according to any of the preceding Claims, c h a r a c t e r i z e d in that it contains nitrification inhibitors, slowly-soluble plant nutrient components, pesticides, growth hormones, or soil-improving components.

21. The utilization of the fertilizing preparation according to any of the preceding Claims 1-18 as a fertilizer by adding it onto soil in the form of a paste or an emulsion.